1, 1-dichloroalkylphosphonates: Convenient starting materials for low-coordinated trivalent phosphorus compounds

Diisopropyl 1,1-dichloroalkylphosphonates bearing various groups (alkyl, aryl, allyl, benzyl, phenylthiolate, trimethylsilyl) in the α-position were reduced to the corresponding primary 1,1-dichlorophosphines by the LiAlH₄-AlCl₃ system in diethyl ether. Subsequent dehydrochlorination with tertiary amines in the presence of trapping dipolar compounds (ethyl diazoacetate or n-hexylazide) led to the expected 1,2,4-diazaphospholes or 3H-1,2,3,4-triazaphospholes.